Use of phosphoramides as water clarifiers

ABSTRACT

THE USE OF PHOSPHORAMIDES, SUCH AS THOSE PREPARED FROM ESTERS OF PHOSPHOROUS ACID AND AMMONIA OR AMINES, AS WATER CLARIFIERS. THESE ARE PARTICULARLY ILLUSTRATED BY PHOSPHORAMIDES, PREPARED BY REACTING DIALKYL PHOSPHITES WITH POLYAMINES.

United States Patent 3,576,741 USE OF PHOSPHORAMIDES AS WATER CLARIFIERSDerek Redmore, Ballwin, Mo., assignor to Petrolite Corporation,Wilmington, Del.

No Drawing. Original application Nov. 25, 1966, Ser. No. 596,798, nowPatent No. 3,524,908. Divided and this application Oct. 17, 1969, Ser.No. 867,374

Int. Cl. C02b N20 US. Cl. 210-54 Claims ABSTRACT OF THE DISCLOSURE Theuse of phosphoramides, such as those prepared from esters of phosphorousacid and ammonia or amines, as water clarifiers. These are particularlyillustrated by phosphoramides, prepared by reacting dialkyl phosphiteswith polyamines.

This application is a division of Ser. No. 596,798 filed Nov. 25, 1966,now US Pat. No. 3,524,908.

This invention relates to phosphoramides. More particularly, thisinvention relates to phosphoramide-esters containing at least one unit.

This invention also relates to uses for phosphoramides, including theiruse as corrosion inhibitors.

These compounds are characterized by at least one i P@ unit, and in thepreferred embodiment by at least one unit,where is an amino-derivedmoiety.

They may be illustrated by the following non-limiting examples where Ais alkylene and R is the alcohol moiety and R' is an amino substitutionand is hydrocarbon, alkyl, etc.

Patented Apr. 27, 1971 ice and n is 1-9, as hereinafter shown in columns3 and 4 in the general formula for the polyalkylene polyamines The alsoinclude polymers, for example including polymeric esters such as etc.,which contain at least one n-Butyl amine Furfurylamine Dibutyl amineDodecylamine Z-ethylhexyl amine Monoethanolamine Di(2-ethylhexyl) amineDiethanolamine Monoisopropanolamine N-methyl ethanolamineDiisopropanolamine N-ethyl ethanolamine n-Amylamine Methylisopropanolamine Di-n-amylamine Butyl isopropanolamine HexylamineSec-amylamine Dihexylamine N-ethylbutylamine Heptylamine2-amino-4-methylpentane Octylamine 4-amino-2-butan0l Dioctylamine5-isopropylamino-l-pentanol Decylamine Similarly, secondary highmolecular weight aliphatic amines known as Armeen 2C and Armeen 2HY canbe used. (RR'NH) Also, high molecular Weight aliphatic amines known asArmeen 10, Armeen 16D, Armeen HTD, Armeen 18D, and Armeen CD can beused. (RNH Suitable amines having an aromatic ring includealphamethylbenzylamine and alpha-methylbenzylmonoethanolamine.

Other amines include:

2-amino-2-methyl-l-propanol 2-amino-2-methyl-1,3-propanediol2-amino-2-ethyl-1,3-propanediol 3-amino-2-methyl-l-propanol2-amino-l-butanol 3-amino-2,2-dimethyl-l-propanol2-amino-2,3-dimethyl-1-propanol 2,2-diethyl-2-amino ethanol2,2-dimethyl-2-amino ethanol 3-amino-1,2-butanediol4-amin0-1,2-butanediQl 2-amino-l,3-butanediol 4-amino-l,3-butanediol2-amino-1,4-butanediol 3-amino-1,4-butanediol 1-amino-2,3-butanediolAmines having ring structures include cyclohexylamine,dicyclohexylamine, and various comparable amines with alkyl substituentsin the ring.

A wide variety of polyamines having at least one amidifiable amino groupcan be employed. These include the polyalkylene polyamines such as ofthe formula:

in which R is hydrogen, alkyl, cycloalkyl, aryl, or aralkyl and R is adivalent radical such as Examples of suitable polyamines include:

Ethylenediamine Diethylenetriamine TriethylenetetramineTetraethylenepentamine Propylenediamine DipropylenetriamineTripropylenetetramine Butylenediamine AminoethylpropylenediamineAminoethylbutylenediamine Other polyamines in which the nitrogen atomsare separated by a carbon atom chain having 4 or more carbon atomsinclude the following: Tetramethylenediamine,

pentamethylenediamine, hexamethylenediamine, etc.

If desired, one can prepare a variety of reactants having two or moreamino groups and at least one hydroxyl group. One may use modificationsof procedures or the procedures themselves as described in US. Pats.Nos. 2,046,720, dated July 7, 1936, to Bottoms; 2,048,990 dated July 28,1936, to Britton et al.; 2,447,821 dated Aug. 24, 1949, to Sankus; and1,985,885 dated Jan. 1, 1935, to Bottoms. Examples include thefollowing:

CHzCHOHCHZNH:

CHzCH;

CH3CHOHCHOHCH2NH CHzCHOHCHOHCHzNH:

Other suitable amines are exemplified by ethylenebisoxypropylamine,

(311 CHzCHzCHzNHz CH O OHzCHzCHzNHz and derivatives obtained by treatingethylenebisoxypropylamine with 1, 2, 3, or 4 moles of ethylene oxide,propylene oxide, butylene oxide, or the like.

Other compounds including those having cyclic structures includepiperazine, and the corresponding derivatives, etc.

Another example of polyamines which may be employed as a reactant is thekind described as Duomeens.

Duomeen is a trademark designation for certain diamines. Duomeen havethe following general formula:

R is an alkyl group derived from a fatty acid or from the mixed fattyacids as obtained from certain oils. The

specific Duomeen and the source of the radical R are as follows:

Duomeen 12-17=lauric Duomeen C-R=coconut oil fatty acid Similarly, acomparable diamine, presumably obtained from Rosin Amine D andacrylonitrile, can be prepared. The structure of Rosin Amine D is asfollows:

( JH OHZNHZ Polyamines from monoamines and cyclic imines, such asethylene imine.

H C uHze-N- C H2 C Hz-N Hz N-tetradeeyl ethylenediamine H C mHgr-N-CHz-CHz-NHz N-hexadecylethylenediarnine H C l2 25-N C a a-N 2 N-dodecylpropylenediamine H C oHn-N- C AHg-NH2 N -decy1 butylenediamine It is tobe noted that all the above examples show high molal groups, i.e., 8carbon atoms or more. The same derivatives in which methyl, ethyl,propyl, butyl, amyl, hexyl groups, or the like, appear instead of octyl,decyl, etc., are equally satisfactory.

Cyclic amidines, such as imidazolines and tetrahydropyrimidines, havingan amino side chain can be reacted, for example N-GH;

ums- N CH;

H 0 2O HEN) H l-polyethylene amine, 2-undecylimidazoline NCH HCH2CH2NCH2CH2N 2 l-(liethylene diamine, 2-heptadecylimidazoli neTetrahydropyrimidines from monocarboxy acids andtrimethylenepolyarnines.

N-O H C17H35C CH2 N -0H (lizH4PNH2 l-aminoethyl,2-heptadecyltetrahydropyrimidine %NCHCH CrzHz5-C CH2 N-Czl-aminoethylaminoethyl, 2-dodecyl, 4-methy1tetral1ydropyrimidine Cyclicamidines are derived conveniently from carboxy acids, includingpolycarboxy acids. As is well known, some polycarboxy acids have 3 ormore carboxyl radicals; thus, it is possible to obtain cyclic amidinesin which 3 or more ring radicals appear.

Cyclic amidines having more than one ring are illustrated by thefollowing formulas:

R=hydrocarbon radical containing 8-32 carbon atoms. Cyclic amidinescontaining basic tertiary amino groups:

Diamides may be obtained from polyamines and two moles of acid.

Polyamides are derived from polycarboxy acids as well as monocarboxyacids. Thus it is possible to get polyamides by using acids containingmore than one carboxyl group, as illustrated in the following examples:

R- (COOH) =Emery dimeric acid available commercially and said to bedilinoleie acid.

Amino amides can be obtained from polyamides in which there is aterminal tertiary amine radical having a basic nitrogen atom. Anotherprocedure involves the production of an amino amide from a polyamine inwhich the terminal radicals are either primary or secondary followed byalkylation of the amide so as to convert the residual terminal radicalinto a basic tertiary amine radical. Another procedure is to use asecondary amine, such as dibutylamine or dihexylamine, and reactstepwise with ethylene irnine or propylene imine. The polyamine soobtained contains a basic tertiary amino radical. The acylation of sucha polyamine results in an amino amide which will form complexescomparable to those obtained from a basic tertiary amine. Examples ofsuch amino amides are as follows:

It is to be noted that all the above examples show high molal groups,i.e., 7 carbon atoms or more. The same derivatives in which methyl,ethyl, propyl, amyl, butyl, hexyl groups, or the like, appear instead ofgroups having 9, 17, 19 carbon atoms or the like, are equallysatisfactory.

Other amines include those of the acrylonitrile andacetonecyanohydrin-polyamine reaction products such as described in thefollowing patent applications: S.N. 502,- 636, filed Oct. 22, 1965, nowU.S. Pat. No. 3,531,496; S.N. 502,447, filed Oct. 22, 1965, now U.S.Pat. No. 3,450,646, issued on June 17, 1969; SN. 520,883, filed Jan. 17,1966, now U.S. Pat. No. 3,488,294, issued on Jan. 6, 1970.

Other amines include hydrazine and derivatives thereof, high molecularweight polyethyleneimines, polypropyleneimines, etc. having molecularweight for example above 1,000, such as 5,000 to over a million, etc.,and other amidifiable amines.

These phosphoramides may be prepared by any suitable means.

The preferred reaction for the preparation of the phosphoric monoamidesinvolves the reaction of an alkyl phosphite with a polyhalide and asecondary or primary amine. The polyhalide and dialkyl phosphite reacttogether under basic catalysis to produce a reactive intermediate whichis readily attacked by the amine to produce the'phosphoric monoamide.Although carbon tetrachloride is the preferred halide in the reaction,other polyhalides such as pentachloro ethane, hexachloroethane, carbontetrabromide, bromoform, iodoform, bromotrichloromethane and others canbe used.

The following examples are presented for purposes of illustration andnot of limitation:

EXAMPLE 1 To diethyl phosphite (27.6 g., 0.2 mole) dissolved in carbontetrachloride ml.) was carefully added diethylene triamine (20 g., 0.2mole) dissolved in carbon tetrachloride (50 ml.) over a period of fiveminutes during which time the temperature rose from room temperature toabove 50 C. After stirring for about six hours at ambient temperature,the product was extracted with water which was evaporated to yield 0 [IH H (EtohP-N- CHzCHzN 2111101 The general reaction can be presented asfollows:

Although the procedure of Example 1 is a very convenient one,alternative procedures can be used with advantage in some cases. The useof a solvent in place of an excess of carbon tetrachloride is aparticularly useful modification and is illustrated in Example 2.Further alternative procedures giving rise to phosphoramides fromphosphites are described in Examples 3 and 4. Other preparations ofphosphoramides, particularly using halides of phosphorus are describedby Koso'lapotf in Organophosphorus Compounds, Wiley, 1950, pp. 278-298.

EXAMPLE 2 To a solution of diethyl phosphite (27.6 g., 0.2 mole) andcarbon tetrachloride (38.5 g., 0.25 mole) in ethyl alcohol (100 ml.) wasadded diethylene triamine (2.6 g., 0.2 mole) in ethyl alcohol (50 ml.).The reaction temperature was maintained at 50-60 by controlling the rateof addition of the amine. After stirring for two hours, evaporation ofthe solvents gave the expected phosphoramide identical with that ofExample 1.

The following example illustrates the use of a tertiary amine to removehydrogen chloride in the reaction of a primary amine with diethylphosphite and carbon tetrachloride.

EXAMPLE 3 To a stirred solution of triethylamine (20.2 g., 0.2 mole) anddiethyl phosphite (27.6 g., 0.2 mole) in carbon tetrachloride (150 ml.),dodecyl amine (37.0 g., 0.2 mole) in carbon tetrachloride (50 ml.) wasadded in 15 minutes to give an exothermic reaction. After stirring atambient temperature for three hours the triethylamine hydrochloride wasremoved by washing with water. Evaporation of the organic extractyielded 63.5 g. (91%) of the phosphoramide.

ll (CzHgOhPNHCnHza.

The following example illustrates the reaction of an amino imidazoline.

EXAMPLE 4 To a solution of diethyl phosphite (0.1 mole) in carbontetrachloride (60 ml.) was added l-p-aminoethyl, Z-octadecylZ-imidazoline (0.1 mole) in 40 ml. of carbon tetrachloride during 30minutes. An exothermic reaction took place yielding the phosphoramide90%.

II N N-CHzOHrNHHOEt);

Since HCl is given off in the reaction, in the case of monoarnines, itis customary to employ two moles of the amine in order to consume theHCl. In the case of polyamines, only one mole is employed since theproduct, being basic, will absorb HCl.

0 ll (ROMP-H NHzCHzOHmH Since the following examples are similarlyprepared, to save repetitive details they will be presented in thefollowing table.

TABLE I Comments M01 Formula Product M01 Amine Phosphite ll 4(CnHuOhPNHz if 5.....- (oiz zsohP 0 O l 1 (C;H O) l NH-(CH )zNHi(OC2H5):Et N 2 mole used to remove H01 as In Ex. 3.

ll 9...... (CzHaO): H

i 10..." (CgHgOhPH ii 11..- (ctHoohPH 15 USE AS CORROSION INHIBITORSThis phase of this invention relates to the use of these compounds ininhibiting the corrosion of metals, most particularly iron, steel andferrous alloys. These compounds can be used in a wide variety ofapplications and systems where iron, steel and ferrous alloys areaffected by corrosion. They may be employed for inhibiting corrosion inprocesses which require a protective or passivating coating as bydissolution in the medium which comes in contact with the metal. Theycan be used in preventing atmospheric corrosion, underwater corrosion,corrosion in steam and hot water systems, corrosion in chemicalindustries, underground corrosion, etc.

The corrosion inhibitors contemplated herein find special utility in theprevention of corrosion of pipe or equipment which is in contact with acorrosive oil-containing medium, as for example, in oil wells producingcorrosive oil or oil-brine mixtures, in refineries, and the like. Theseinhibitors may, however, be used in other systems or applications. Theyappear to possess'properties which impart to metals resistance to attackby a variety of corrosive agents, such as brines, Weak inorganic acids,organic acids, CO H S, air or oxygen, etc.

The method of carrying out this process is relatively simple inprinciple. The corrosion preventive reagent is dissolved in the liquidcorrosive medium in small amounts and is thus kept in contact with themetal surface to be protected. Alternatively, the corrosion inhibitormay be applied first to the metal surface, either as is, or as asolution in some carrier liquid or paste. Continuous application, as inthe corrosive solution, is the preferred method, however.

The present process finds particular utility in the protection of metalequipment of oil and gas wells, especially those containing or producingan acidic constituents such as H S, CO air or oxygen, organic acids andthe like. For the protection of such wells, the reagent, eitherundiluted or dissolved in a suitable solvent, is fed down the annulus ofthe well between the casing and producing tubing where it becomescommingled with the fluid in the well and is pumped or flowed from thewell with these fluids, thus contacting the inner Wall of the casing,the outer and inner wall of tubing, and the inner surface of allwellhead fittings, connections and flow lines handling the corrosivefluid.

Where the inhibitor composition is a liquid, it is conventionally fedinto the well annulus by means of a motor driven chemical injector pump,or it may be dumped periodically (e.g., once every day or two) into theannulus by means of a so-called boll weevil device or similararrangement. Where the inhibitor is a solid, it may be dropped into thewell as a solid lump or stock, it may be blown in as a powder with gas,or it may be washed in with a small stream of the well fluids or otherliquid. Where there is gas pressure on the casing, it is necessary, ofcourse, to employ any of these treating methods through a pressureequalizing chamber equipped to allow introduction of reagent into thechamber, equalization of pressure between chamber and casing, and travelof reagent from chamber to well casing.

Occasionally, oil and gas wells are completed in such a manner thatthere is no opening between the annulus and the bottom of the tubing orpump. This results, for example, when the tubing is surrounded at somepoint by a packing held by the casing or earth formation below thecasing. In such wells the reagent may be introduced into the tubingthrough a pressure equalizing vessel, after stopping the flow or fluids.After being so treated, the well should be left closed in for a periodof time suflicient to permit the reagent to drop to the bottom of thewell.

For injection into the well annulus, the corrosion inhibitor is usuallyemployed as a solution in a suitable solvent. The selection of solventwill depend much upon the specific reagent being used and its solubilitycharacteristics.

For treating Wells with packed-01f tubing, the use of solid sticks orplugs of inhibitor is especially convenient. These may be prepared byblending the inhibitor with a mineral wax, asphalt or resin in aproportion sufficient to give a moderately hard and high-melting solidwhich can be handled and fed into the well conveniently.

The protective action of the herein described reagents appears to bemaintained for an appreciable time after treatment ceases, buteventually is lost unless another application is made.

For example, for the protection of gas wells and gascondensate wells,the amount of corrosion inhibitor used might range between about A to 3lbs. per million cubic feet of gas produced, depending upon the amounts.and composition of corrosive agents in the gas and the amount of liquidhydrocarbon and water produced. However, in no case does the amount ofinhibitor required appear to be stoichiometrically related to the amountof acids produced by a well, since protection is obtained with much lesscorrosion inhibitor than usually would be required for neutralization ofthe acids produced.

These compounds are particularly effective in the prevention ofcorrosion in systems containing a corrosive aqueous medium, and mostparticularly in systems containing brines.

These reagents can also be used in the prevention of corrosion in thesecondary recovery of petroleum by water flooding and in the disposal ofwaste water and brine from oil and gas wells. Still more particularly,they can be used in a process of preventing corrosion in water floodingand in the disposal of waste water and brine from oil and gas wellswhich is characterized by injecting into an underground formation anaqueous solution containing minor amounts of the compositions of thisinvention, in suflicient amounts to prevent the corrosion of metalsemployed in such operation.

When an oil well ceases to flow by the natural pressure in the formationand/or substatnial quantities of oil can no longer be obtained by theusual pumping methods, various processes are sometimes used for thetreatment of the oil-bearing formation in order to increase the flow ofoil. These processes are usually described as secondary recoveryprocesses. One such process which is used quite frequently is the waterflooding process wherein water is pumped under pressure into what iscalled an injection well and oil, along with quantities of water, thathave been displaced from the formation, are pumped out of an adjacentWell usually referred to as a producing well. The oil which is pumpedfrom the producing well is then separated from the water that has beenpumped from the producing well and the water is pumped to a storagereservoir from which it can again be pumped into the injection well.Supplementary water from other sources may also be used in conjunctionwith the produced water. When the storage reservoir is open to theatmosphere and the oil is subject to aeration this type of waterflooding system is referred to herein as an open water flooding system.If the water is recirculated in a closed system Without substantialaeration, the secondary recovery method is referred to herein as aclosed Water flooding system.

Because of the corrosive nature of oil field brines, to economicallyproduce oil by water flooding, it is necessary to prevent or reducecorrosion since corrosion increases the cost thereof by'making itnecessary to repair and replace such equipment at frequent intervals.

I have discovered a method of preventing corrosion in systems containinga corrosive aqueous media, and most particularly in systems containingbrines, which is characterized by employing the compounds describedherein. For example, I have discovered an improved process of protectingfrom corrosion metallic equipment employed in secondary oil recovery bywater flooding such as injection wells, transmission lines, filters,meters, storage tanks, and other metallic implements employed thereinand particularly those containing iron, steel, and ferrous alloys, suchprocess being characterized by employing in water floood operation anaqueous solution of the compositions of this invention.

The invention, then, is particularly concerned with preventing corrosionin a water flooding process characterized by the flooding medium,containing an aqueous or an oil field brine solution of these reagents.

In many oil fields large volumes of water are produced and must bedisposed of where water flooding operations are not in use or wherewater flooding operations cannot handle the amount of produced water.Most states have laws restricting pollution of streams and land withproduced waters, and oil producers must then find some method ofdisposing of the waste produced salt water. In many instances therefore,the salt water is disposed of by injecting the water into permeable lowpressure strata below the fresh Water level. The formation into whichthe water is injected is not the oil producing formation and this typeof disposal is defined as salt water disposal or waste water disposal.The problems of corrosion of equipment are analogous to thoseencountered in the secondary recovery operation by water flooding.

The compounds of this invention can also be used in such water disposalwells thus providing a simple and economical method of solving thecorrosion problems encountered in disposing of unwanted water.

Water flood and waste disposal operations are too well known to requirefurther elaboration. In essence, the flooding operation is effected inthe conventional manner except that the flooding medium contains a minoramount of these compounds, suflicient to prevent corrosion.

While the flooding medium employed in accordance with the presentinvention contains water or oil field brine and the compounds of thisinvention, the medium may also contain other materials. For example, theflooding medium may also contain other agents such as surface activeagents or detergents which aid in wetting throughout the system and alsopromote the desorption of residual oil from the formation, sequesteringagents which prevent the deposition of calcium and/or magnesiumcompounds in the interstices of the formation, bactericides whichprevent the formation from becoming plugged through bacterial growth,tracers, etc. Similarly, they may be employed in conjunction with any ofthe operating techniques commonly employed in water flooding and waterdisposal processes, for example five spot flooding, peripheral flooding,etc. and in conjunction with other secondary recovery methods.

The concentration of the corrosion inhibitors of this invention willvary widely depending on the particular compound, the particular system,etc. Concentrations of at least about A p.p.m., such as about to 7,500p.p.m. for example about 1 to 5,000 ppm, advantageously about to 1,000p.p.m., but preferably about 250 p.p.m. may be employed. Larger amountscan also be employed such as 15-50% although there is generally nocommercial advantage in so doing.

For example, since the success of a water flooding operation manifestlydepends upon its total cost being less than the value of the additionaloil recovered from the oil reservoir, it is quite important to use aslittle as possible of these compounds consistent with optimum corrosioninhibition. Since these compounds are themselves inexpensive and areused in low concentrations, they enhance the success of a floodoperation by lowering the cost thereof.

By varying the constituents of the composition, the compounds of thisinvention can be made more oil or more water soluble, depending onwhether the composition is to be employed in oil or water systems.

Although the manner of practicing the present invention is clear fromthe foregoing description, the following non-limiting specific examplesare included for purposes of illustration.

18 EXAMPLES These tests were run under conditions so set up as tosimulate those found in an actual producing well. The test procedureinvolved the measurement of the corrosive action of fluids inhibited bythe compositions herein described upon sandblasted SAE 1020 steelcoupons measuring A1 inch in diameter and being 4 inches long whencompared to test coupons containing no inhibitor and commercialinhibitors.

Clean pint bottles were half-filled (almost 200 ml.) with seawater (i.e.tap water containing 3% by Weight of the salts, magnesium chloride,calcium chloride, sodium sulfate and sodium chloride) which had beensaturated with hydrogen sulfide. Those requiring inhibitor were chargedwith the same by pipetting calculated amounts contained in suitablesolvents .(water, isopropyl alcohol, mineral spirits) to give therequired parts per million of inhibitor. Uninhibited blanks were run inconjunction with inhibited solutions. The bottles were now filled (totalvolume now about 400 ml.) leaving a small air space to allow forexpansion. The weighed coupons attached to scaling caps were screwedonto the botles and they were placed on a rotating Wheel for seven daysat 115 F. The coupons were then removed, cleaned electrolytically in 5%sulfuric acid (using the coupons as a cathode) and washed successivelywith dilute sodium hydroxide, twice water, once with acetone and finallydried.

When the inhibitor was oil-soluble as contrasted to Water-soluble, atwo-phase system was used instead of the all-brine system and thissimply consisted of using hydrogen sulfide saturated mineral spirits toreplace 25% by volume of the brine.

The changes in the weights of the coupons during the corrosion test weretaken as a measurement of the effectiveness of the inhibitorcompositions. Protective percent age was calculated for each test coupontaken from the inhibited fluids in accordance with the followingformula:

X percent protection 1 in which W is the loss in weight of the coupontaken from uninhibited fluids and W is the loss in weight of couponswhich were subjected to inhibited fluids.

The results obtained are presented in the following Table II.

All of the compositions prepared in Examples 1-27 are excellentcorrosion inhibitors when tested and compared with the commercialcorrosion inhibitors previously selected as the best commercialinhibitors for the corrosion system. The following examples arepresented as exemplary.

TABLE IL-HzS SYSTEM Percent protection at various p.p.m.

It is well known that most corrosion inhibitors of the film-forming ornon-reducing type are not too effective in preventing corrosion inaerobic systems, i.e. containing air and/or oxygen. However, thecompounds of this invention are particularly suitable for preventingcorrosion in aerobic systems. For example, they are particularlysuitable for systems containing oxygen such as found in open secondaryrecovery systems, cooling towers, and the like.

In this test one follows the procedure employing coupons of the typeused for the H 5 test, fitted into the cap of a bottle having a capacityof 1000 ml. The bottles are 19 filled with 800 ml. of liquid and rockedduring the test period. Instantaneous corrosion rates are measured usingthe corrosion meter described in S.N. 332,399 filed Dec. 23, 1963, nowU.S. Pat. No. 3,406,101, issued on Oct. 15, 1968.

TEST 1.AIR SATURATED SEAWATER, 115 F.

Concen- Corrosion tration, r e, Compound p.p.m. mils/year Example 1- 10016. 8 Example 27.... 100 10.2 Unlnhlbited 29. 4

TEST 2.10% BRINE-AIR STANDARD-115 F.

Concen- Corrosion tratlon, rate,

Compound p.p.m. mils/year Example 17- 10 18. Example 17..-- 1,000 11. 2Uninhlbited 22. 6

WATER CLARIFICATION The present invention also relates to a method forthe clarification of water containing suspended matter.

Accordingly clarification of water containing suspended particles ofmatter is effected by adding to such water compounds of this invention.

Water containing suspended particles which may be treated by the presentinvention may have its origin either in natural or artificial sources,including industrial and sanitary sources. Waters containing suspendedparticles of natural origin are usually surface waters, wherein theparticles are suspended soil particles (silt), although subsurfacewaters may also be treated according to the present invention. Waterhaving its origin in industrial process (including sanitary water)operations may contain many different varieties of suspended particles.These particles are generally the result of the particular industrial orsanitary operation concerned. Prior to discharging such industrial wastewaters into natural water courses it generally is desired that thesuspended matter be removed.

The present process may likewise be applied to water contained in stockor fish ponds, lakes or other natural or artificial bodies of watercontaining suspended solids. It may be applied to industrial watersupplied either in preparation therefor, during or after use and priorto disposal. It may be applied to sanitary water supplies either for theelimination of suspended solids prior to use for such purposes, or itmay be applied to such waters which have become contaminated withimpurities from any source.

Most naturally occurring waters contain an amount of simple electrolytes(sodium, potassium, ammonium, calcium, aluminum salts, etc.) in excessof that necessary for the initial aggregation of the ultimate siltparticles. This is likewise true of particles of suspended material inindustrial or sanitary waters. The ultimate particles of silt or othermaterials are therefore naturally somewhat aggregated by reason of thepresence of such electrolytes. However, the forces binding such ultimateparticles together are not great and moreover are not such as togenerally effect either rapid settling rates of the fluocculatedmaterial or strong enough to prevent deflocculation.

The compounds of this invention cause rapid flocculation and alsoreinforce the formed aggregates of particles causing a generaltightening or bonding together of the initial particles and an increasedrate of coagulation and settling, thus forming a less turbid supernatantliquid.

The addition of the compounds of this invention to the water suspensionshould be made in such a fashion that the resulting flocculation andaggregation of the particles takes place uniformly throughout the bodyof water. In order to obtain a uniform addition of the compositions ofthe invention to the waterborne suspension it is generally desirable toprepare a relatively dilute stock solution of the compositions and thento add such solution to the body of water in the proportions indicated.Clarification may take place either in the natural body of water or itmay be caused to take place in hydraulic thickeners of known design.

The amount of the compositions to be employed will vary depending uponthe amount and the degree of subdivision of the solids to beagglomerated or flocculated, the chemical nature of such solid and theparticular inventive compositions employed. In general, I employ atleast a s-uflicient amount of the compositions to promote flocculation.In general, I employ 0.005-10,000 p.p.m. or more such as about 0.51,000p.p.m., for example about 1- 500 p.p.m., but preferably about 2-5 p.p.m.Since the economics of these processes are important, no more than theminimum amount required for efficient removal is generally employed. Itis desired, of course, to employ sufficient compositions so flocculationwill take place without causing the formation of stable dispersions.

The precipitating action of the compositions can be employed in theapplication of loading or filling materials to textiles or paper.

In the processing of fine mineral particles in aqueous suspension theflocculating agents will be especially useful. In the processing of oresto separate valuable mineral constituents from undesirable matrixconstituents, it is frequent practice to grind the ore into afinely-divided state to facilitate separation steps such as selectiveflotation and the like. In many ore dressing procedures, thefinely-divided ore is suspended in water to form a pulp or slime. Afterprocessing, it is usually desirable to dewater the pulps or slimeseither by sedimentation or filtering. In such operations, certain oresare particularly troublesome in that the finely-divided ore, whensuspended in water, forms a stable slime which settles very slowly, ifat all. Such slimes are unsuitable for concentration or dewatering bysedimentation and are difficult to dewater by filtration because of thetendency to clog the pores of the filter, thus leading to excessivelytime-consuming and inefiicient operation of the filters. In some cases,for example, in certain phosphate mining operations, the formation ofvery stable suspensions of finely-divided mineral results not only inthe loss of considerable valuable mineral as waste but also requireslarge expenditures for the maintenance of holding ponds for the waste.Similar problems are involved in processing gold, copper, nickel, lead,zinc, iron, such as taconite ores, uranium and other ores, and theinventive flocculating agents will be useful in these operations.

Some sepcific additional applications for the compositions of thisinvention, not intended to be limiting but merely illustrative arelisted below. The compositions can be used for the clarification ofbeers or wines during manufacture. Another use is in processingeflluents in pharmaceutical operations for the recovery of valuableproducts or removal of undesirable by-products. A particularly importantuse for these flocculating agents is in the clarification of both beetsugar and cane sugar juices in their processing, Still another use isfor flocculation and recovery of pigments from aqueous suspensionsthereof. The compositions will be particularly useful in sewagetreatment operations as a flocculating agent. A further use is topromote by flocculation the removal of coal from aqueous suspensionsthereof. In other words, the flocculating agents of the invention aregenerally useful for processing aqueous effiuents of all types tofacilitate the removal of suspended solids.

A water soluble or water dispersible compound, to the extent ofeffective concentration, is employed.

These compositions can also be employed in the process of flocculatingwhite water and/or recyling of the precipitate solids in the papermaking process described in U.S. application S.N. 347,023, filed Feb.24, 1964, now abandoned, and other processes described therein.

Although the manner of practicing the present invention is clear fromthe foregoing description, the following non-limiting specific examplesare included for purposes of illustration.

Naturally occurring water from many sources, and in some instances,brine and brackish waters are used in the recovery of petroleum bysecondary water-flooding operations. Clarification of the water isnecessary in many instances prior to Water flooding because thesuspended impurities tend to plug the underground formations into whichwaters are pumped.

EXAMPLES A suspension of FeS in brine was subjected to the action of thewater-soluble compounds prepared herein.

In these tests, the FeS concentration is 25 parts per million and 1% andbrine solution were used. Metered quantities (500 ml.) of thehomogeneous suspension were placed into 1000 ml. beakers and stirred at100 r.p.m. The compound to be tested was injected into the suspension togive final active concentrations varying between 2 through 4 parts permillion. A commercial flocculant was run simultaneously at equivalentconcentrations for comparison and the stirring was achieved by use of aPhipp and Bird floc multi-stirrer. After one minute the stirring ratewas reduced to 20 to 30 r.p.m. and maintained thus for ten minutes. Atthis time the stirring was stopped. The evaluation of the compoundstarted at the moment of flocculation and continued with respect to thefloc size and rate of precipitation. The final evaluation was achievedby visual examination of the color of the resultant aqueous phase.

The results obtained by employing the water-so1uble compounds of TableI, i.e. Examples 1, 2, 4, 7 through 11, 13 through 20, 22 through 24, 26and 27, are found to be superior to the commercial flocculating agentusually employed.

These compounds are also effective in flocculating the other systemsdescribed herein.

The following is a partial list of industrial systems in which thecompounds of the present invention can be employed as flocculatingagents.

( 1) Petroleum industry (2) Food industry such as in the dairy industry,the canning, freezing and dehydration industries (3) Metal platingindustry (4) Chemical and pharmaceutical industries (5) Mining industry,for example, in the phosphate mining industry such as in phosphateslimes (6) Fermentation industries, such as in alcohol, beer,

yeast, antibiotics, etc. production (7) Tanning industry (8) Meatpacking and slaughter house industry (9) Textile industry (10) Sugarrefining industry (11) Coal industry (12) Soap industry (13) Sewagepurification (14) Corn starch industry (15) Fat processing and soapindustry (16) Paper industry (17) Hydroelectric plants, atomic energyoperations,

boiler plants, etc.

OTHER DERIVATIVES These products may be further reacted to formderivatives thereof, for example, they may be oxyalkylated with alkyleneoxides such as ethylene oxide, propylene oxide,

22 butylene oxide, octylene oxide, alone or in combination; with styreneoxide, glycide, methyl glycide, allyl glycidyl ether, glycidyl isopropylether, glycidyl phenylether, diepoxides, polyepoxides, etc.

They may be reacted with alkylene imines such as ethyleneimine,propylene imine, etc., dialkylaminoepoxypropane of the structure wherethe Rs are alkyl, etc.

They may be acylated with monocarboxylic acids, such as aromatic acids,fatty acids, aliphatic acids, etc. and polycarboxylic acids aliphaticdicarboxylic acids, aromatic dicarboxylic acids for example diglycolic,phthalic, succinic, etc., acids.

These compounds may also be treated with more than one agent, forexample, they may be partially acylated, then oxyalkylated, partiallyoxyalkylated then acylated, etc.

They may be alkylated, quaternized, used to prepare salts of organicacids, etc.

OTHER USES In addition to the uses described above, these compositionsand/or derivatives thereof, can be used as follows:

(1) as demulsifiers for water-in-oil and oil-in-water emulsrons (2) asbiocides i.e. bacteriocides, algicides, etc.

(3) as additives to various petroleum fuels including gasoline, dieselfuel, jet fuels, etc.

(4) as gasoline anti-icers and anti-stallers (5) as flotation agents,such as flotation collection agents (6) as emulsifiers, for example, inmetal cleaners, auto polishes, wax emulsions, etc.

(7) as additives for sludging oil and cutting oils 8) as fuel dehazingagents (9) as agents for preparing emulsions for the Hydrafrac processof enhancing oil recovery (10) as agents to prepare polymer emulsions(11) as agents for the textile industry such as mercerizing assistants,wetting agents, rewetting agents, penetrating agents, dispersing agents,softening agents, dyeing assistants, etc.

(12) as anti-static agents for textiles, plastics, etc.

(13) as agents in leather processing (14) as lube oil additives (15 asemulsifiers for insecticidal and agricultural compositions (16) asadditives for rubber latices, for example, to prevent acid coagulation(17 as additives in the production of latex foam rubber, for example, asgel sensitizers and processing aids in the manufacture of foam rubber(18) as additives for primer paints to help insure adhesion to metallicsurfaces and give corrosion protection (19) as additives useful as afreeze-thaw stabilizer for latex-base paints (20) as agents for the pulpand paper industry, such as sizing aids, etc.

(21) as general metal deactivators (22) scale inhibitors Having thusdescribed my invention what I claim as new and desire to obtain byLetters Patent is:

1. A process of water clarification comprising adding to watercontaining suspended matter a phosphoramide prepared by reacting (1) anester of the formula where R is the alcohol moiety employed in formingsaid ester from phosphorus acid and (2) ammonia, an amine or a mixtureof amines.

2. The process of claim 1 wherein (2) is a polyamine.

3. The process of claim 1 wherein R is a C H C H C 'H or HCECOHFradical.

4. A process of water clarification comprising adding to watercontaining suspended matter a polymeric phos- 5 phoramide prepared byreacting -(1) a polymeric ester of the formula where 15 A is an alkyleneradical, n is about 1 to 50 and m is about 2 to 40 and (2) ammonia, anamine or a mixture of amines. 20

5. The process of claim 4 wherein (2) is a polyamine. 6. The process ofclaim 4 wherein A is -CH CH 7. The process of claim 1 wherein (2) is amixture of polyalkylene polyamines.

2'4 8. The process of claim 3 wherein (2) is a polyamine of the formulaH NH2(AN)1-10H where A is ethylene or propylene.

9. The process of claim 3 wherein the amine in (2) is a polyamine of theformula References Cited UNITED STATES PATENTS 3/1939 Flint et a1260--959 FOREIGN PATENTS 8/1958 Australia 210-54 OTHER REFERENCESAtherton et a1., Jour. Of The Chem. Soc. (London) pp. 660-663 (1945).

MICHAEL ROGERS, Primary Examiner

